WO2009142009A1 - Electrode pour une batterie secondaire au lithium et batterie secondaire au lithium équipée de celle-ci - Google Patents

Electrode pour une batterie secondaire au lithium et batterie secondaire au lithium équipée de celle-ci Download PDF

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Publication number
WO2009142009A1
WO2009142009A1 PCT/JP2009/002222 JP2009002222W WO2009142009A1 WO 2009142009 A1 WO2009142009 A1 WO 2009142009A1 JP 2009002222 W JP2009002222 W JP 2009002222W WO 2009142009 A1 WO2009142009 A1 WO 2009142009A1
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WIPO (PCT)
Prior art keywords
active material
current collector
electrode
material body
lithium secondary
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PCT/JP2009/002222
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English (en)
Japanese (ja)
Inventor
山本泰右
八木弘雅
宇賀治正弥
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パナソニック株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by パナソニック株式会社 filed Critical パナソニック株式会社
Priority to CN2009801181321A priority Critical patent/CN102037585A/zh
Priority to US12/993,712 priority patent/US20110070492A1/en
Priority to JP2009537829A priority patent/JP4422207B2/ja
Publication of WO2009142009A1 publication Critical patent/WO2009142009A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0435—Rolling or calendering
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49108—Electric battery cell making
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49108—Electric battery cell making
    • Y10T29/49115—Electric battery cell making including coating or impregnating

Definitions

  • the present invention relates to an electrode for a lithium secondary battery and a lithium secondary battery including the same.
  • Patent Document 1 by the present applicant proposes an electrode in which an active material layer having a plurality of columnar active material bodies is formed on a current collector surface.
  • the plurality of active material bodies are arranged at intervals on the current collector surface.
  • Such an electrode deposits an evaporated deposition material (for example, silicon) on a current collector having a plurality of convex portions on the surface from a direction inclined with respect to the normal direction of the current collector surface (oblique deposition). ).
  • silicon is easily incident on and deposited on the convex portion of the surface of the current collector, and is difficult to deposit on the shadowed portion of the convex portion (and the material deposited on the convex portion).
  • gap which absorbs the volume expansion of an active material body can be ensured between adjacent active material bodies.
  • Patent Document 2 proposes forming a cut in the active material layer by applying a tensile load to the current collector after forming the active material layer on the current collector.
  • Patent Document 2 describes that the cut formed in the active material layer becomes a void for relaxing the expansion stress of the active material, and the charge / discharge cycle characteristics can be improved.
  • step (A) since the active material body is formed on each convex portion of the current collector, a void can be formed between adjacent active material bodies. Thereafter, in step (B), the gap between the active material bodies can be further expanded by stretching the current collector on which the active material bodies are formed. For this reason, it becomes possible to form a space sufficient to alleviate the expansion of the active material caused by charging and discharging.
  • a larger gap can be formed between the active material bodies. become.
  • the proportion of voids can be increased as compared with the conventional case. Therefore, when an active material body expand
  • FIG. 1 It is typical sectional drawing which illustrates the manufacturing method of the conventional electrode using oblique vapor deposition.
  • (A) And (b) is typical sectional drawing for demonstrating the vapor deposition process and extending
  • (A)-(d) is typical process sectional drawing for demonstrating the vapor deposition process in the manufacturing method of the electrode of embodiment by this invention.
  • (A) And (b) is the top view and sectional drawing which illustrate the electrical power collector used by embodiment by this invention, respectively. It is sectional drawing for demonstrating the vapor deposition apparatus used at the vapor deposition process in embodiment by this invention.
  • (A) to (c) are diagrams schematically showing a current collector after an active material layer is formed in the electrode manufacturing method according to the embodiment of the present invention.
  • FIGS. 4A and 4B are cross-sectional views taken along lines II ′ and II-II ′ shown in FIG. 4C, respectively, and FIG. (A)-(c) is a figure which shows typically the electrode 200 obtained by the manufacturing method of the electrode of embodiment by this invention, (a) and (b) are shown to (c), respectively.
  • a sectional view taken along line II ′ and II-II ′, FIG. It is the schematic which shows the cylindrical battery using the electrode of this invention.
  • (A)-(c) is typical process sectional drawing for demonstrating the manufacturing method of the electrical power collector in an Example and a comparative example. It is a top view which shows the surface shape of the electrical power collector in an Example and a comparative example.
  • FIG. 6 is a diagram for explaining a stretching process of Example 2.
  • FIG. It is a figure for demonstrating the other extending
  • FIG. 1 is a schematic cross-sectional view illustrating a conventional electrode manufacturing method using oblique deposition.
  • 2A and 2B are schematic cross-sectional views for explaining the outline of the vapor deposition process and the stretching process in the present embodiment, respectively.
  • the cross-section including the deposition direction of the conventional electrode shown in FIG. Compare.
  • the evaporated deposition material for example, silicon
  • the evaporated deposition angle is a predetermined angle with respect to the normal D of the surface of the current collector 11 (hereinafter referred to as “deposition angle”).
  • the light is incident on the surface of the current collector 11 from a direction 52 inclined by ⁇ .
  • the 1st part 14a of the active material body containing silicon is formed on each convex part 12 (the 1st step
  • FIG. 5 is a schematic view illustrating the configuration of a vapor deposition apparatus used for forming the active material body.
  • the vapor deposition apparatus 40 includes a vacuum chamber 41 and an exhaust pump 47 for exhausting the vacuum chamber 41. Inside the vacuum chamber 41, a fixing base 43 for fixing the current collector 11, a gas introduction pipe 42 for introducing oxygen gas into the chamber 41, and evaporation for supplying silicon to the surface of the current collector 11.
  • a crucible 46 loaded with a source is installed.
  • silicon can be used as the evaporation source.
  • an electron beam heating means for evaporating the material of the evaporation source is provided.
  • the gas introduction pipe 42 includes an oxygen nozzle 45, and is positioned so that oxygen gas injected from the oxygen nozzle 45 is supplied near the surface of the current collector 11.
  • the fixed base 43 and the crucible 46 are arranged so that vapor deposition particles (here, silicon atoms) 49 from the crucible 46 are in the direction of the angle (deposition angle) ⁇ with respect to the normal direction D of the current collector 11. It arrange
  • the “horizontal plane” refers to a plane perpendicular to the direction in which the material of the evaporation source loaded in the crucible 46 is vaporized and directed to the fixing base 43.
  • the growth direction S 1 of the first portion 14 a is inclined by the angle ⁇ 1 with respect to the normal direction D of the current collector 11.
  • silicon atoms 49 are incident and simultaneously oxygen gas is supplied from the oxygen nozzle 45 toward the current collector 11.
  • silicon oxide (SiO x ) is selectively deposited on the first portion 14a of the current collector 11, and the second portion 14b is obtained.
  • the angle ⁇ of the fixing base 43 is again returned to the same angle as the first stage vapor deposition step (here, 65 °), and the same as the first stage vapor deposition step. Silicon oxide may be grown under the conditions (third vapor deposition step).
  • the third portion 14c is further formed on the second portion 14b.
  • the inclination angle ⁇ 3 in the growth direction S 3 of the third portion 14c is the same as the inclination angle ⁇ 1 of the first portion 14a.
  • FIGS. 6A, 6B, and 6C are diagrams schematically showing the current collector after the active material body is formed and before being stretched.
  • 6C is a plan view
  • FIGS. 6A and 6B are cross-sectional views taken along lines I-I ′ and II-II ′ shown in FIG. 6C, respectively.
  • the plurality of active material bodies 14 obtained by the above vapor deposition step are regularly arranged corresponding to the positions of the convex portions 12 shown in FIG. 4 as shown in FIG. These active material bodies 14 do not contact each other, and a gap 16 a exists between the active material bodies 14.
  • a layer including a plurality of active material bodies 14 and voids 16a between adjacent active material bodies 14 is referred to as an active material layer 15a.
  • Each active material body 14 may have a zigzag shape corresponding to the growth direction S, but here has an upright columnar shape along the normal direction D of the current collector 11.
  • the upright columnar active material body 14 is obtained. Even in such a case, it can be confirmed by the cross-sectional observation of the active material body 14 that the growth direction S of the active material body 14 extends in a zigzag shape from the bottom surface to the top surface.
  • FIGS. 7A, 7B, and 7C are diagrams schematically showing the electrode 200.
  • FIG. FIG. 7C is a plan view
  • FIGS. 7A and 7B are cross-sectional views taken along lines I-I ′ and II-II ′ shown in FIG. 7C, respectively.
  • the linear voidage (minimum linear voidage) (Lb2 / Lb1) ⁇ 100 (%) in the direction 18 of the electrode 200 is larger than the minimum linear voidage (La2 / La1) ⁇ 100 (%) before stretching. .
  • a sufficient space for relaxing expansion and contraction of the active material body 14 can be ensured more reliably.
  • a battery is comprised using the electrode extended
  • the current collector 11 on which the active material layer 15a is formed may be stretched at least in a uniaxial direction on a plane parallel to the surface of the current collector 11.
  • the stretching method is not particularly limited, but it is preferable to apply a load uniformly in the stretching direction.
  • a sheet-like current collector for example, when winding the current collector on which the active material layer is formed from one roller to the other roller, the current collector is applied by applying a load between the two rollers. Can be stretched in the longitudinal direction (MD direction).
  • the TD direction it may be stretched.
  • the film may be stretched in the biaxial direction on a plane parallel to the surface of the current collector 11.
  • it may be stretched by applying a tensile load in two axial directions (for example, the MD direction and the TD direction) orthogonal to each other simultaneously or sequentially.
  • stretch by performing the rolling process with respect to the electrical power collector 11 in which the active material body 15a was formed. An apparatus used for this method will be described later.
  • the current collector 11 is stretched so that the length in the stretching direction of the current collector 11 is 100.5% or more of the length of the current collector 11 in the stretching direction before stretching. It is preferable to stretch 11. This is because, by plastically deforming the current collector 11 so as to have a length of 100.5% or more, voids that can sufficiently relieve stress due to expansion and contraction can be formed between the active material members 14.
  • the “plastic deformation” refers to a deformation remaining without returning to the original state after applying a load exceeding the elastic limit of the material and releasing the load, and does not include elastic deformation. Therefore, “stretching the current collector 11 by plastic deformation” means that the current collector 11 is held in a stretched state after the current collector 11 is deformed by applying a tensile load and the tensile load is removed. Means.
  • the elongation rate (breaking elongation rate) of the current collector 11 before stretching is preferably 1.0% or more.
  • “Elongation rate (breaking elongation rate)” refers to the elongation rate when a tensile test is performed to break. When the current collector 11 having a breaking elongation of 1.0% or more is used, it becomes easier to stretch the current collector 0.5 by 0.5% or more without causing the current collector 11 to be cut.
  • An annealing process may be performed on the current collector 11 before performing the stretching step. Thereby, since the breaking elongation rate of the current collector 11 can be increased, the current collector 11 is easily stretched.
  • the annealing process is not essential regardless of the type of the current collector 11, the effect of the present invention can be obtained more reliably by performing the annealing process.
  • the annealing treatment are not particularly limited, and may be appropriately selected depending on the material of the current collector 11 and the like.
  • linear porosity and “minimum linear porosity” are respectively the linear porosity and the minimum linear porosity of the active material layer 15b after the electrode 200 is produced and before lithium is occluded. Refers to the average value.
  • the linear porosity or the minimum linear porosity before or after lithium is occluded is determined by observing the upper surface of the active material layer 15b using, for example, a scanning electron microscope (SEM).
  • the electrode 200 Since the electrode 200 is stretched in advance, deformation such as wrinkles hardly occurs due to charging / discharging of the battery. Even in a battery using a conventional electrode that has not been previously stretched, the electrode is stretched in a plane parallel to the current collector by charge and discharge. However, a portion of the current collector where the active material layer is not formed (such as a lead wire extraction portion) hardly extends. On the other hand, in the battery using the electrode 200 of the present embodiment, the portion of the current collector of the electrode 200 where the active material layer is not formed is also stretched. Therefore, in order to determine whether or not the electrode has been stretched in the electrode production stage, in addition to the presence or absence of wrinkles on the electrode after charge and discharge, for example, the elongation of the lead wire extraction portion may be examined.
  • the convex portion 12 is a columnar body having a rhombus-shaped upper surface, but the shape of the convex portion 12 is not limited to this.
  • the orthographic projection image of the convex portion 12 viewed from the normal direction D of the current collector 11 is a square, a rectangle, a trapezoid, a rhombus, a parallelogram, a polygon such as a pentagon and a home plate, a circle, an ellipse, or the like. May be.
  • the shape of the cross section parallel to the normal line direction D of the current collector 11 may be a square, a rectangle, a polygon, a semicircle, or a combination thereof.
  • vertical with respect to the surface of the electrical power collector 11 may be a polygon, a semicircle, an arc shape etc., for example.
  • the boundary between the convex portion 12 and a portion other than the convex portion also referred to as “groove”, “concave portion”, etc.), such as when the cross-section of the concavo-convex pattern formed on the current collector 11 has a curved shape.
  • a portion having an average height or more of the entire surface having the concavo-convex pattern is defined as “convex portion 12”, and a portion less than the average height is defined as “groove” or “concave portion”.
  • the “concave portion” may be a single continuous region as in the illustrated example, or may be a plurality of regions separated from each other by the convex portion 12.
  • the “interval between adjacent convex portions 12” in this specification is a distance between adjacent convex portions 12 on a plane parallel to the current collector 11, and is defined as “groove width” or “recessed portion It shall refer to “width”.
  • the height H of the convex portion 12 is preferably 3 ⁇ m or more, more preferably 4 ⁇ m or more, and even more preferably 5 ⁇ m or more. If the height H is 3 ⁇ m or more, the active material body 14 can be disposed only on the convex portion 12 by utilizing the shadowing effect when forming the active material body 12 by oblique vapor deposition. A gap 16 can be secured between the fourteen.
  • the height H of the convex portion 12 is preferably 15 ⁇ m or less, more preferably 12 ⁇ m or less. If the convex part 12 is 15 micrometers or less, since the volume ratio of the electrical power collector 11 which occupies for an electrode can be restrained small, it becomes possible to obtain a high energy density.
  • the convex portions 12 are preferably arranged regularly at a predetermined arrangement pitch, and may be arranged in a pattern such as a staggered lattice pattern or a grid pattern.
  • the arrangement pitch of the protrusions 12 (the distance between the centers of the adjacent protrusions 12) is, for example, 10 ⁇ m or more and 100 ⁇ m or less.
  • “the center of the convex portion 12” refers to the center point of the maximum width on the upper surface of the convex portion 12. If the arrangement pitch is 10 ⁇ m or more, a space for expanding the active material bodies 14 can be ensured more reliably between the adjacent active material bodies 14. Preferably it is 20 micrometers or more, More preferably, it is 30 micrometers or more.
  • the arrangement pitch P is 100 ⁇ m or less
  • a high capacity can be secured without increasing the height of the active material body 14.
  • it is 80 micrometers or less, More preferably, it is 60 micrometers or less, More preferably, it is 50 micrometers or less.
  • the convex portions 12 are arranged along three directions, and it is preferable that the arrangement pitches P a , P b , and P c in the respective directions are within the above range.
  • the ratio of the distance d of the convex portion 12 with respect to the arrangement pitch P a of the convex portion 12 is 1/3 or more than 2/3.
  • the ratio of the intervals e and f of the convex portions 12 to the arrangement pitches P b and P c of the convex portions 12 is also 1/3 or more and 2/3 or less. If the ratios of these intervals d, e, and f are 1/3 or more, when the active material bodies 14 are formed on the respective convex portions 12, the active material bodies 14 in the respective arrangement directions of the convex portions 12 Since the gap width can be ensured more reliably, a sufficient linear void ratio can be obtained. On the other hand, when the ratio of the distances d, e, and f is larger than 2/3, the active material is also deposited in the grooves between the convex portions 12, and the expansion stress applied to the current collector 11 may increase. .
  • the width on the upper surface of the convex portion 12 is preferably 200 ⁇ m or less, more preferably 50 ⁇ m or less. Thereby, since it becomes possible to ensure sufficient space
  • the width of the upper surface of the convex portion 12 is more preferably 2 ⁇ m or more, whereby the deformation of the convex portion 12 due to charge / discharge can be more reliably suppressed.
  • the widths a, b, and c of the upper surface of the convex portions 12 along each arrangement direction are all within the above range.
  • the distances d, e, and f between the adjacent convex parts 12 are the width a, It is preferably 30% or more of b and c, more preferably 50% or more. Thereby, a sufficient space
  • the intervals d, e, and f are the widths of the convex portions 12, respectively. It is preferably 250% or less of a, b and c, more preferably 200% or less.
  • the upper surface of the convex portion 12 may be flat, but preferably has irregularities, and the surface roughness Ra is preferably 0.1 ⁇ m or more.
  • “Surface roughness Ra” here refers to “arithmetic mean roughness Ra” defined in Japanese Industrial Standards (JISB 0601-1994), and can be measured using, for example, a surface roughness meter. If the surface roughness Ra of the upper surface of the convex portion 12 is less than 0.1 ⁇ m, for example, when a plurality of active material bodies 14 are formed on the upper surface of one convex portion 12, the width (column) of each active material body 14 (Diameter) becomes small, and is easily destroyed during charging and discharging.
  • the thickness is 0.3 ⁇ m or more, whereby the active material body 14 can easily grow on the convex portion 12, and as a result, a sufficient gap can be reliably formed between the active material bodies 14.
  • the surface roughness Ra is preferably, for example, 30 ⁇ m or less. More preferably, it is 10 micrometers or less, More preferably, it is 5.0 micrometers or less. In particular, when the surface roughness Ra of the current collector 11 is in the range of 0.3 ⁇ m or more and 5.0 ⁇ m or less, the adhesive force between the current collector 11 and the active material body 14 can be sufficiently secured. 14 can be prevented from peeling.
  • the material of the current collector 11 is preferably copper or a copper alloy produced by, for example, a rolling method or an electrolytic method, and more preferably a copper alloy having a relatively high strength.
  • the current collector 11 in this embodiment is not particularly limited, for example, a regular uneven pattern including a plurality of convex portions 12 is formed on the surface of a metal foil such as copper, copper alloy, titanium, nickel, and stainless steel. Obtained by.
  • metal foil metal foil, such as rolled copper foil, rolled copper alloy foil, electrolytic copper foil, electrolytic copper alloy foil, is used suitably, for example.
  • the thickness of the metal foil before the concave / convex pattern is formed is not particularly limited, but is preferably 1 ⁇ m or more and 50 ⁇ m or less, for example. If it is 50 micrometers or less, since a collector will become thin, the ratio of the active material which occupies for an electrode will become high, and the capacity
  • the thickness of the metal foil is more preferably 6 ⁇ m or more and 40 ⁇ m or less, and further preferably 8 ⁇ m or more and 33 ⁇ m or less.
  • a method for forming the convex portion 12 is not particularly limited. For example, etching using a resist resin or the like is performed on the metal foil to form a groove with a predetermined pattern on the metal foil, and a portion where the groove is not formed is formed. It is good also as the convex part 12.
  • the active material member 14 in the present embodiment grows along the direction S inclined with respect to the normal direction D of the current collector 11.
  • the angle (inclination angle) ⁇ formed between the growth direction S and the normal direction D of the active material body 14 is preferably 5 ° or more, and more preferably 10 ° or more.
  • the contact area between the active material body 14 and the current collector 11 is large, that is, the inclination angle may be 0 °. Therefore, no gap can be formed between the adjacent active material bodies 14. However, if the angle is 5 ° or more, a sufficient contact area can be obtained while forming a gap between the active material bodies 14.
  • the inclination angle ⁇ may be less than 90 °, but the vapor deposition efficiency decreases as it approaches 90 °. Therefore, in consideration of productivity, the inclination angle is preferably 80 ° or less.
  • the inclination angle ⁇ of the active material body 14 is determined by the vapor deposition angle when the active material body 14 is formed.
  • the inclination angle ⁇ can be obtained, for example, by measuring the inclination angle of any 2 to 10 active material members 14 and calculating the average value of these values.
  • the inclination angle ⁇ of the active material body 14 may change with the height of the active material body 14.
  • all the growth directions S in the active material body 14 are inclined with respect to the normal direction D.
  • the inclination angle ⁇ is preferably 10 ° or more and less than 90 °.
  • the ratio of the area of the void 16b in the active material layer 15b is preferably 5% or more and 50% or less. If the surface porosity is 5% or more, the expansion and contraction of the active material body 14 can be effectively absorbed by the gaps 16b, so that the deformation of the electrode 200 can be reduced. On the other hand, from the viewpoint of securing a high capacity, the surface porosity is preferably 50% or less. In addition, when each active material body 14 is a columnar body upstanding along the normal line D on the surface of the current collector 11, the surface porosity is viewed from the normal line D on the surface of the current collector 11.
  • each active material body 14 is a columnar body tilted in one direction or a zigzag columnar body, the respective areas of the active material layer 15b and the gap 16b are obtained in a cross section parallel to the surface of the current collector 11. Is calculated by
  • the thickness t of the active material layer 15 b is equal to the height of the active material body 14, and is along the normal direction of the current collector 11 from the upper surface of the convex portion 12 of the current collector 11 to the top of the active material body 14.
  • the distance t is indicated, for example, 0.01 ⁇ m or more, preferably 0.1 ⁇ m or more.
  • capacitance characteristic of the active material containing silicon can be utilized.
  • the thickness t is, for example, 3 ⁇ m or more, the volume ratio of the active material in the entire electrode is increased, and a higher energy density is obtained. More preferably, it is 5 micrometers or more, More preferably, it is 8 micrometers or more.
  • the thickness t of the active material layer 15b is, for example, 100 ⁇ m or less, preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less.
  • the expansion stress due to the active material layer 15b can be suppressed, and the current collection resistance can be lowered, which is advantageous for high-rate charge / discharge.
  • the thickness t is, for example, 30 ⁇ m or less, more preferably 25 ⁇ m or less, the deformation of the current collector 11 due to the expansion stress can be more effectively suppressed.
  • the thickness t of the active material layer 15b can be measured by, for example, the following method. First, the thickness of the entire electrode 200 after forming the active material layer 15b is measured. When the convex portion 12 and the active material layer 15 b are formed only on one surface of the current collector 11, the thickness of the current collector 11 including the convex portion 12 (metal foil) is calculated based on the thickness of the entire electrode 200. The thickness t of the active material layer 15b can be obtained by subtracting the sum of the thickness of the protrusion 12 and the height of the protrusions 12).
  • the thickness of the current collector 11 including the convex portion 12 (the thickness of the metal foil)
  • the total thickness of the active material layers 15b formed on both surfaces of the current collector 11 is obtained by subtracting the sum of the total height of the convex portions 12 formed on both surfaces thereof.
  • the thickness (width) of the active material member 14 is not particularly limited, but is preferably 100 ⁇ m or less, more preferably 50 ⁇ m, in order to prevent the active material member 14 from cracking due to expansion during charging. It is as follows. In order to prevent the active material body 14 from peeling from the current collector 11, the width of the active material body 14 is preferably 1 ⁇ m or more.
  • the thickness of the active material body 14 is, for example, a surface of any 2 to 10 active material bodies 14 that is parallel to the surface of the current collector 11 and is 1 ⁇ 2 of the height t of the active material body 14. It is calculated
  • the capacity per unit area of the active material layer 15b is preferably 2 mAh / cm 2 or more, whereby high battery energy can be obtained.
  • the capacity per unit area is increased while ensuring a linear porosity of 5% or more, the thickness (height of the active material body 14) t of the active material layer 15b increases and the amount of expansion during charging increases. Therefore, there is a possibility that deformation of the current collector 12 due to expansion stress cannot be sufficiently suppressed.
  • capacitance per unit area is preferably 10 mAh / cm 2 or less, more preferably 8 mAh / cm 2 or less.
  • the active material layer 15b in the present embodiment preferably contains a silicon element or a tin element, thereby ensuring a high capacity. More preferably, an active material containing silicon element is included.
  • the active material layer 15b may include, for example, at least one selected from the group consisting of silicon alone, a silicon alloy, a compound containing silicon and oxygen, and a compound containing silicon and nitrogen.
  • the active material layer 15b may include only one type of the above materials, or may include two or more types of materials.
  • the compound containing silicon and nitrogen may further contain oxygen.
  • the active material layer 15b may be formed of a plurality of compounds containing silicon, oxygen, and nitrogen and having different molar ratios of these elements, or a plurality of silicon oxides having different molar ratios of silicon to oxygen. It may be formed from a composite of things.
  • the active material layer 15b includes silicon oxide (SiO x , where 0 ⁇ x ⁇ 2).
  • SiO x silicon oxide
  • oxygen ratio the molar ratio of the oxygen amount to the silicon amount
  • the charge / discharge capacity decreases.
  • the average value of the oxygen ratio x is greater than 0, the expansion and contraction associated with charging / discharging is suppressed, so that the expansion stress applied to the current collector 11 can be suppressed.
  • the average value of the oxygen ratio x is less than 1.5, sufficient charge / discharge capacity can be secured and high rate charge / discharge characteristics can be maintained. Therefore, good charge / discharge cycle characteristics and high reliability can be realized.
  • the oxygen ratio in each part having different growth directions may be different from each other. Even in such a case, the average value of the oxygen ratio x of the entire active material layer 15b may be 0 ⁇ x ⁇ 2, and preferably 0 ⁇ x ⁇ 1.5.
  • the “average value of the molar ratio x of the oxygen amount to the silicon amount” in the active material layer 15b is a composition excluding lithium supplemented or occluded in the active material layer 15b.
  • the active material layer 15b should just contain the silicon oxide which has said oxygen ratio, and may contain impurities, such as Fe, Al, Ca, Mn, and Ti.
  • FIG. 8 is a schematic cross-sectional view of a cylindrical battery using the electrode 200 of the present embodiment.
  • the cylindrical battery 80 includes a cylindrical electrode group 84 and a battery can 88 that accommodates the cylindrical electrode group 84.
  • the electrode group 84 is obtained by winding a belt-like positive electrode plate 81 and a belt-like negative electrode plate 82 together with a wide separator 83 disposed therebetween.
  • the positive electrode plate 81 includes a positive electrode current collector and a positive electrode active material layer formed on the positive electrode current collector
  • the negative electrode plate 82 includes a negative electrode current collector and a negative electrode current collector formed on the negative electrode current collector. And an active material layer.
  • the configuration of the negative electrode plate 82 is the same as that of the electrode 200 described above with reference to FIGS. 7A and 7B, for example.
  • the negative electrode plate 82 and the positive electrode plate 81 are disposed so that the negative electrode active material layer and the positive electrode active material layer face each other with the separator 83 interposed therebetween.
  • the electrode group 84 is impregnated with an electrolyte (not shown) that conducts lithium ions.
  • the opening of the battery can 88 is closed by a sealing plate 89 having a positive electrode terminal 85.
  • One end of an aluminum positive electrode lead 81 a is connected to the positive electrode plate 81, and the other end is connected to the back surface of the sealing plate 89.
  • An insulating packing 86 made of polypropylene is disposed on the periphery of the sealing plate 89.
  • One end of a copper negative electrode lead (not shown) is connected to the negative electrode plate 82, and the other end is connected to the battery can 88.
  • An upper insulating ring (not shown) and a lower insulating ring 87 are disposed above and below the electrode group 84, respectively.
  • the positive electrode active material layer releases lithium ions during charging, and occludes lithium ions released by the negative electrode active material layer during discharge.
  • the negative electrode active material layer occludes lithium ions released by the positive electrode active material during charging, and releases lithium ions during discharge.
  • components other than the negative electrode plate 82 in the lithium ion secondary battery 80 are not particularly limited.
  • lithium-containing transition metal oxides such as lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), and lithium manganate (LiMn 2 O 4 ) can be used for the positive electrode active material layer.
  • the positive electrode active material layer may be composed of only the positive electrode active material, or may be composed of a mixture containing the positive electrode active material, the binder, and the conductive agent.
  • the positive electrode active material layer may be comprised from several active material body like the negative electrode active material layer. Note that a metal such as Al, an Al alloy, or Ti is preferably used for the positive electrode current collector.
  • lithium ion conductive solid electrolytes and non-aqueous electrolytes are used as the lithium ion conductive electrolyte.
  • the non-aqueous electrolyte a solution obtained by dissolving a lithium salt in a non-aqueous solvent is preferably used.
  • the composition of the nonaqueous electrolytic solution is not particularly limited.
  • the separator and the outer case are not particularly limited, and materials used in various forms of lithium secondary batteries can be used without particular limitation. Instead of the separator, a solid electrolyte having lithium ion conductivity may be used, or a gel electrolyte containing such a solid electrolyte may be used.
  • FIG. 8 shows an example of a cylindrical battery having a wound electrode group
  • the battery of the present invention may be a wound prismatic battery or a coin-type stacked battery. May be.
  • the stacked battery may have a structure in which a positive electrode and a negative electrode are stacked in three or more layers.
  • a positive electrode having a positive electrode active material layer on both sides or one side so that all positive electrode active material layers face the negative electrode active material layer and all negative electrode active material layers face the positive electrode active material layer;
  • the slanted state of the active material body (growth direction, number of vapor deposition stages, growth direction of the portion obtained by each vapor deposition process, etc.) is the same for all negative electrode active material layers. It may be different for each negative electrode active material layer.
  • active material bodies having different inclination states may be formed in the same negative electrode active material layer.
  • the inclined states of the active materials in the negative electrode active material layers on the respective surfaces may be the same or different.
  • each component of the lithium secondary battery of the present invention is not particularly limited except that the electrode of the present invention is used as a negative electrode or a positive electrode, and is generally used as a material for a lithium ion battery. Various types can be selected.
  • Example 1 and comparative example Hereinafter, Example 1 and a comparative example of the electrode according to the present invention will be described.
  • the electrode 1 was produced as Example 1 and the electrode A was produced as a comparative example, and the porosity of each active material layer was measured.
  • Electrode fabrication method (i-1) Electrode 1 ⁇ Preparation of current collector> First, a method for manufacturing the current collector used in the electrode 1 will be described.
  • Roughening treatment was carried out by electrolytic plating on both surfaces of a 27 ⁇ m thick copper foil (HCL-02Z, manufactured by Hitachi Cable Ltd.) to form copper particles having a particle diameter of 1 ⁇ m.
  • a roughened copper foil 93 having a surface roughness Rz of 1.5 ⁇ m is obtained.
  • the surface roughness Rz refers to the ten-point average roughness Rz defined in Japanese Industrial Standard (JISB 0601-1994). Instead, a roughened copper foil commercially available for a printed wiring board may be used.
  • a plurality of grooves (concave portions) 94 were formed on the ceramic roller 90 using laser engraving.
  • the plurality of grooves 94 were diamond-shaped when viewed from the normal direction of the ceramic roller 90.
  • the lengths of the diagonal lines of the rhombus were 10 ⁇ m and 20 ⁇ m, the distance along the diagonal line a of the adjacent concave portion 94 was 18 ⁇ m, and the distance along the diagonal line b was 20 ⁇ m.
  • the depth of each recessed part 94 was 10 micrometers.
  • a rolling process was performed by passing the copper foil 93 at a linear pressure of 1 t / mm between the ceramic roller 90 and another roller (not shown) arranged to face the ceramic roller 90.
  • a current collector 91 having a plurality of convex portions 92 on the surface was obtained as shown in FIG.
  • region pressed by parts other than the recessed part 94 of the ceramic roller 90 among the copper foil 93 which passed between rollers was planarized so that it might illustrate.
  • the height of the convex portion 92 was smaller than the depth of the concave portion 94 of the ceramic roller 90 and was about 6 ⁇ m.
  • FIG. 1 A plan view of the current collector 91 is shown in FIG.
  • the shape and arrangement of the convex portions 92 of the current collector 91 correspond to the concave portions 94 formed in the ceramic roller 90.
  • the upper surface of the convex part 92 was substantially rhombus, and the lengths a and b of the diagonal lines were about 10 ⁇ m and about 20 ⁇ m, respectively. Further, the interval e along the diagonal line a between adjacent convex portions 92 was 18 ⁇ m, and the interval d along the diagonal line b was 20 ⁇ m.
  • ⁇ Deposition process> The current collector 91 obtained by the above method was placed on the fixed base 43 disposed inside the vacuum chamber 41 described above with reference to FIG. Then, while supplying oxygen gas with a purity of 99.7% to the vacuum chamber 41, EB deposition using silicon as the evaporation source was performed using an evaporation unit (a unit of evaporation source, crucible and electron beam generator). It was. At this time, the inside of the vacuum chamber 41 was an oxygen atmosphere having a pressure of 3.5 Pa. Further, in order to evaporate silicon of the evaporation source, the electron beam generated by the electron beam generator was deflected by the deflection yoke and irradiated to the evaporation source. As the evaporation source, scrap material (scrap silicon, purity: 99.999%) generated when a semiconductor wafer was formed was used.
  • the fixing base 43 was tilted so that the vapor deposition angle ⁇ was 65 °, and the first vapor deposition step was performed in this state to form the first-stage portion (first portion) of the active material body.
  • the deposition rate of the first part was about 8 nm / s, and the oxygen flow rate was 30 sccm.
  • the height of the first part was 0.4 ⁇ m.
  • vapor deposition was performed from the direction parallel to the shorter diagonal of each convex part 12 in the surface parallel to the surface of the electrical power collector 91.
  • the fixing base 43 is rotated clockwise around the central axis, and is inclined in a direction opposite to the inclination direction of the fixing base 43 in the first stage vapor deposition step, so that the vapor deposition angle ⁇ is ⁇ 65 °. .
  • vapor deposition was performed with an oxygen flow rate of 25 sccm to form a second part (second vapor deposition step).
  • the tilting direction of the fixing base 43 was changed again to the same direction as the first stage vapor deposition process, and the same vapor deposition was performed with the vapor deposition angle ⁇ of 65 ° and the oxygen flow rate of 20 sccm (third vapor deposition process). .
  • the oxygen flow rate was gradually reduced to 15th step, 15 sccm, 10 sccm, 5 sccm, 1 sccm up to the seventh step, Vapor deposition was performed without introducing oxygen from the stage to the 35th stage to form an active material body having a height of 14 ⁇ m, and an active material layer (thickness t: 14 ⁇ m) was obtained.
  • the average value of the molar ratio x of the oxygen amount to the silicon amount in the active material layer was 0.4.
  • the current collector 91 was removed from the fixing base 43, and the current collector 91 was again placed on the fixing base 43 so that the surface (back surface) opposite to the surface on which the active material layer was formed was up. 35 steps of vapor deposition steps were performed on the back surface of the current collector 91 in the same manner as described above to form an active material layer (thickness t: 14 ⁇ m) (not shown). In this way, active material layers were formed on both surfaces of the current collector 91.
  • Extension process> In performing the stretching step, first, the breaking strength and breaking elongation of the current collector 91 before stretching were determined.
  • the current collector 91 having an active material layer formed on both sides was cut into a size of 15 mm in width and 70 mm in length, and stretched in a uniaxial direction until the current collector 91 was broken by a tensile test.
  • the stretching direction was the direction along the longer diagonal line b of each convex portion 92, and the tensile speed was the lowest speed.
  • the breaking strength was 11.2 N / mm and the breaking elongation (maximum elongation) was 0.2%.
  • an annealing treatment was performed at 500 ° C. for 1 hour.
  • the current collector 91 after the annealing treatment was cut into a size having a width of 15 mm and a length of 70 mm, and similarly stretched in the uniaxial direction until it was broken by a tensile test.
  • the breaking strength was 6.1 N / mm
  • the breaking elongation was 8%.
  • the current collector 91 after the annealing treatment may be stretched at a rate smaller than 8%, which is the elongation at break. I understood.
  • the current collector 91 after the annealing treatment is cut into a size having a width of 15 mm and a length of 70 mm, and the current collector 91 is cut into the longer diagonal line b of each convex portion 92 using a tensile tester.
  • the length along the stretching direction was extended by 5% by plastic deformation. Thereby, the electrode 1 was obtained.
  • FIG. 11 and FIG. 12A are schematic views showing the results of observing the electrode A and the electrode 1 from the normal direction of the current collector, respectively, using a scanning electron microscope.
  • FIG. 12B is an enlarged view of FIG.
  • a direction parallel to the vapor deposition direction is X
  • a direction perpendicular to the direction X is Y.
  • the directions X and Y are parallel to the diagonal lines a and b (FIG. 10) of the convex portion 12 of the current collector 91.
  • the width WX in the X direction and the width WY in the Y direction of each active material body when the electrode A and the electrode 1 are viewed from the normal direction of the current collector. Since the arrangement pitch PX along the X direction, the arrangement pitch PY along the Y direction, the linear porosity (minimum linear porosity) in the direction Z connecting the closest active material bodies, and the surface porosity were determined. It is shown in 1.
  • the widths WX and WY of the active material bodies hardly extend by the stretching process, but the arrangement pitch PY of the active material bodies extends about 20%, and the gaps between the active material bodies are in the Y direction. You can see that it has expanded. It can also be seen that the minimum linear porosity and the surface porosity can be expanded to 19.4% and 31.9%, respectively.
  • the ratio of voids between the active material bodies can be increased and the expansion stress can be reduced without reducing the productivity.
  • the void ratio can be adjusted as appropriate by changing conditions such as tensile load.
  • an active material silicon oxide
  • FIG. 12 (b) it can be seen that there is a break in this deposited layer by the stretching process. Most of the cuts occur along the direction X perpendicular to the stretching direction. Therefore, even if the active material of the deposited layer expands, these cuts become voids, and the stress applied to the current collector 91 due to the expansion can be reduced.
  • Example 2 In Example 1 described above, the current collector was stretched along the Y direction. However, in Example 2, the current collector on which the active material layer was formed was stretched by rolling, and the electrode 2 was stretched. Produced.
  • an active material layer was formed on both sides of the current collector in the same manner as in Example 1 using the same current collector as in Example 1. Thereafter, annealing was performed in an argon atmosphere at a temperature of 500 ° C. for 1 hour in the same manner as in Example 1. The current collector after the annealing treatment was cut into a size having a width of 15 mm and a length of 70 mm.
  • the current collector on which the active material layer was formed was stretched on the surface parallel to the current collector.
  • the current collector was stretched by a rolling process using a stretchable rubber.
  • FIG. 13 is a schematic cross-sectional view for explaining the stretching process (rolling process) performed in Example 2.
  • a current collector (15 mm ⁇ 70 mm) 100 on which an active material layer is formed is sandwiched between two rubber plates 63 having a thickness of 1.0 mm, and the current is collected via the plates 63.
  • the body 100 was pressurized along its thickness direction.
  • silicone rubber SR50 manufactured by Tigers Polymer Co., Ltd. was used as the extensible rubber used for the plate 63.
  • the current collector 100 was stretched in all directions in a plane parallel to the surface of the current collector 100. In this way, an electrode 2 was obtained.
  • Example 2 when the electrode 2 was observed from the normal direction of the current collector using a scanning electron microscope, it was confirmed that the electrode 2 was extended not only in the Y direction but also in the X direction.
  • the surface porosity of the active material layer of the electrode 2 was 28%.
  • variety (thickness) of an active material body hardly changed by the extending process, and the space
  • Example 2 the current collector 100 was fixed and the rolling process was performed.
  • the rolling process is performed using an apparatus as shown in FIG. Also good. Specifically, first, the current collector 100 is sandwiched between two rubber plates 63. Next, the current collector 100 is pulled in the direction of the arrow while compressing the current collector 100 using the roller 61 from the surface opposite to the side in contact with the current collector 100 of each plate 63. Thereby, the sheet-like current collector 100 can be rolled continuously and efficiently.
  • the rubber to be used is not particularly limited as long as it has stretchability.
  • the current collector 100 can be extended in a uniaxial direction.
  • the current collector 100 is biaxial. Can stretch in the direction.
  • the negative electrode for a lithium secondary battery of the present invention can be applied to various lithium secondary batteries such as a coin shape, a cylindrical shape, a flat shape, and a square shape. These lithium secondary batteries have charge / discharge cycle characteristics superior to conventional ones while ensuring a high charge / discharge capacity. Therefore, it can be widely used in portable information terminals such as PCs, mobile phones, and PDAs, and audiovisual equipment such as video recorders and memory audio players.
  • Electrode 11 91 Current collector 12, 92 Projection 14 Active material body 15a, 15b Active material layer 16a, 16b Void D Normal direction of current collector surface S Growth direction of active material body 41 Vacuum chamber 42 Gas introduction pipe 43 fixed base 46 crucible 45 oxygen nozzle 49 silicon atom 50 horizontal plane

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Abstract

La présente invention concerne un procédé de production d'une électrode pour une batterie secondaire au lithium. Le dit procédé comprend un procédé (A) dans lequel un matériau vaporisé pour un dépôt en phase vapeur sur la surface d'un collecteur (11) présentant sur la surface une pluralité de parties soulevées (12) est dirigé à partir d'une direction (52) inclinée par rapport à la direction normale (D) de la surface du collecteur (11) afin de former une substance active (14) sur la pluralité de parties soulevées (12) du collecteur (11), et un procédé (B) dans lequel le collecteur (11) sur lequel la matière active (14) a été formée est tiré au moins de manière uniaxe dans une direction parallèle à la surface du collecteur (11).
PCT/JP2009/002222 2008-05-20 2009-05-20 Electrode pour une batterie secondaire au lithium et batterie secondaire au lithium équipée de celle-ci WO2009142009A1 (fr)

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US12/993,712 US20110070492A1 (en) 2008-05-20 2009-05-20 Electrode for a lithium secondary battery and lithium secondary battery equipped with same
JP2009537829A JP4422207B2 (ja) 2008-05-20 2009-05-20 リチウム二次電池用電極の製造方法

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WO2015167302A1 (fr) * 2014-04-30 2015-11-05 한국기계연구원 Procédé de fabrication de structure d'électrode pour dispositif de stockage d'énergie souple, structure d'électrode ainsi fabriquée, et dispositif de stockage d'énergie incluant ladite structure

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JP6887088B2 (ja) * 2017-04-04 2021-06-16 パナソニックＩｐマネジメント株式会社 積層型全固体電池およびその製造方法
JP7208277B2 (ja) * 2021-01-27 2023-01-18 プライムプラネットエナジー＆ソリューションズ株式会社 電極製造装置および電極製造方法

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